Liquid or paste soap preparations having sulfo fatty acid salts as viscosity reducing agents



United States Patent Ofifice 3,377,289 Patented Apr. 9, 1968 3,377,289 LIQUID R PASTE SOAP PREPARATIONS HAV- ING SULFO FATTY ACID SALTS AS VISCOSITY REDUCING AGENTS Werner Stein, Erkrath-Unterbach, Herbert Weiss, Co-

logne-Deutz, and Peter Neuhausen, Krefeld-Fischeln, Germany, assignors to Henl-rel & Cie., G.m.b.H., Dusseldorf-Holthausen, Germany, a corporation of Germany N0 Drawing. Filed Jan. 4, 1965, Ser. No. 423,355 Claims priority, application Germany, Jan. 10, 1964, H 51,322 14 Claims. (Cl. 252109) Liquid or paste combinations of detergent substances are used for the manufacture of compositions for treating different kinds of sOlid materials, as well as the manufacture of liquid detergents and cleansers. These compositions can be used as household cleaners, detergents, dish- Washing compounds, cleaners for polished or lacquered surfaces, floor cleaners, wall-covering cleaners, and the like. These compositions may also be used in industrial applications for cleaning or otherwise treating the surfaces of solid materials, such as in laundries, manufacturing plants, and the like, and usually contain, in addition to soap, various accompanying substances originating in their manufacture and conventional additives.

The viscosity of such concentrated liquid or paste detergent compositions is undesirably increased by the soap content, and often may be further increased by the addition of accompanying substances. Such high-viscosity compositions are hard to handle; for example, it is diflicult to measure and dilute them rapidly. Also, in the industrial manufacture of solid detergents and cleansers, especially those in pourable, granulated form, the viscosity of the pastes from which they are made may be undesirably high when they are to be conveyed from place to place, especially when, after the customary additives, if any, are worked in, they are transformed by conventional methods into pourable, granulated products.

It is therefore an object of this invention to provide a novel composition and method for reducing the viscosity of the saponaceous combinations of detergent substances in liquid or paste form to facilitate their use in various surface treating or cleaning applications and the manufacture of surface-active compounds in dry pourable granulated form.

It has now been found that the viscosity of detergent solutions of pastes containing soaps and, if desired, synthetic detergents, wherein the viscosity is at least 50 cp., can be reduced by the addition of salts of alpha-sulfofatty acids having to 12 carbon atoms in the sulfofatty acid radical. A di-salt particularly effective comprises the disalt of sulfoluaric acid. The addition of alpha-sulfofatty acid salts may be effected in any manner desired. The viscosity reduction, however, of the preparations containing these fatty acid salts in comparison with those that do not depends upon the manner in which the fatty acid salts are added and especially the order in which the individual components are put together in the manufacture of the solutions or pastes.

Since the sulfofatty acid salts are very diflicultly soluble, their ability to reduce the viscosities of soap pastes or solutions is completely unexpected. Other components dissolved in the paste have an effect on its viscosity, in addition to the ester salts and the di-salts, especially the inorganic salts. The viscosity reduction in soap pastes or solutions by the addition of sulfofatty acid compositions is also found in preparation containing salts.

The viscosity reduction of the invention, achieved by addition of the above-defined sulfofatty acid salts, can be observed over a broad viscosity range. The invention is important in the liquefaction of viscous solutions or pastes, such as those having a viscosity of at least 10 cp., or from 50 to 20,000, and preferably from to 10,000 op. The viscosity of pastes in which the sulfofatty acids of this invention are effective can run even higher.

The teachings of the present invention are also applicable to liquid or paste soap preparations with a sulfofatty acid ester content, since the viscosity-reducing effect is also apparent in these mixtures. In US. Patent 2,303,- 212, soap preparations are described which contain amounts of surface-active esters of high sulfofatty acids; however, sulfofatty acids or their salts are not discussed, and, furthermore, the viscosity-reducing effect of sulfofatty acid compositions containing 10 to 12 carbon atoms in the molecule are not taught.

Hereinafter, for the sake of simplicity, the sulfofatty acids or their salts (mono and/or di-salts) are referred to as di-salts, the sulfofatty acid ester salts as ester salts and any wash-active substances not pertaining to the di-salts, ester salts or soaps as WAS. The expression total WAS relates to the sum of soap-s, di-salts and any ester salts or WAS that may be present.

The di-salts to be used according to the invention, which have 10 to 12 carbon atoms in the molecule, may be mixed with higher and possibly also with lower homologs, providing the properties of this mixture are determined substantially by the C and/or C percentage. This is the case with a C and/or C di-salt content of 50 to 65 weight percent (with reference to the total amount of di-salts present) if the rest of the di-salt consists of at least 2, and preferably at least 3, individual disalts which differ in relation to chain length and/or the structure of the sulfofatty acid radical. If the content of C and/or C di-salt is greater than 65 percent of the weight of the total di-salts present, the properties of this mixture are again determined to a great extent by the percentage of C and/or C di-salts, if the balance consists of only one individual di-salt. Di-salts of such composition are obtained preferably from the hardened fatty acids of coconut or palm nut oil, or from the C to C fraction of such oils. However, di-salts of fatty acids of synthetic origin are also usable, and they may also be branched.

The viscosity-reducing effect of the di-salts is apparent at low concentrations, for example, 4 weight percent, and becomes more apparent in the case of higher concentrations', for example, 7 weight percent. However, substantially larger quantities of di-salts may be present, for example, up to 60 weight percent, but preferably 10 to 30 weight percent is suitable.

These weight percentages relate to the total mixture of di-salts, soap and any ester salt that may be present. The viscosity-reducing effect appears also when other washactive substances than those named hitherto are present, but their quantity is not to be greater than that of the soap, the soap content of the mixture amounting to at least 25 weight percent and preferably at least 50 weight percent of the total WAS. When other WAS and/or ester salts are present, the di-salt is to amount preferably to at least 3 Weight percent of the total WAS.

The quantity data on the di-salts relate to the C to C component; if lower or higher di-salt homologs are present, they are reckoned as wash-active substances.

The viscosity-reducing effect of the di-salts becomes perceptible in the case of soaps made from straightchained or branched saturated or unsaturated fatty acids of many different carbon numbers, since the chain length and constitution of the soap fatty acid radical does have some influence on the viscosity. In general, pastes made of unsaturated and/or branched fatty acids are less viscous than those made of fatty acids with a straight and/or saturated carbon chain. But a difference is also observed with different carbon chains: soaps made of fatty acids with 10 to 14 carbon atoms, or of fatty acid mixtures consisting mainly of such fatty acids, are transformed at high concentrations into viscous pastes more rapidly than soaps made from fatty acids with at least 16 carbon atoms per fatty acid radical, or with soaps made of fatty acid mixtures which contain similar or identical fatty acids. In the manufacture of saponaceous detergents and cleaning agents fatty acid and/or mixtures having 10 to 31, and preferably 12 to 18 carbon atoms per fatty acid radical, and an unsaturated fatty acid content of at most 50 weight percent, are of special interest. Preferably, the iodine number of these fatty acids is less than 40, and preferably less than 30. Such fatty acid mixtures may have different chain length percentages, depending on the planned application: for example, the percentage of C to C and preferably of C may be greater than 50 weight percent; but the C to C percentage can be greater even than 65 percent. For low-sudsing detergents, soaps made of fatty acids comprising more than 50 percent saturated fatty acids with 16 to 18 carbon atoms, and also approximately to 60 percent of saturated fatty acids with 20 to 31, and preferably 20 to 24 carbon atoms, have been proposed, especially in combination with other wash-active substances.

The natural fats and the fatty acids obtained therefrom are of particular interest for the manufacture of such soaps. The fatty acids can originate from plant or animal fats. Those fatty acids are particularly suitable which are ordinarily used for the manufacture of soap cakes, powdered soap products or lubricating soaps, as for example soaps made from coconut and palm nut oil, palm oil, peanut oil, rape oil, cottonseed oil, tallow, train oils and fish oils, and their fractions and! or hydrogenation products and/ or mixtures.

These salt-like wash-active substances including the soaps are available preferably as water-soluble salts, e.g., as salts of the alkalies, especially potassium and sodium or triethanolamine. For the manufacture of WAS cornbinations containing practically no undissolved components, it is advantageous in some instances to use a mixture of cations; for example, sodium and potassium salts, or potassium and triethanolamine salts, or sodium, potassium and triethanolamine salts can be used together.

The surface-active ester salts of sulfofatty acids described in US Patent 2,303,212 may also be present in the preparations according to the invention. They are preferably the esters of sulfa-fatty acids with to 22, and preferably 12 to 18 carbon atoms, and monovalent aliphatic alcohols containing 1 to 4 carbon atoms. The chain-length percentages of the sulfo-fatty acid radicals can be adapted to the planned application of the preparations. Ester salts having preferably 10 to 14 carbon atoms in the sulfo-fatty acid radical exhibit good solubility and sudsing properties even at room temperature, while those with preferably 16 to carbon atoms in the fatty acid radical are not easily soluble until higher temperatures are reached, but then they develop an excellent washing ability. The chain-length range of the fatty acids in the" soaps and of the sulfo-fatty acids in the ester salts can be equal or different. For example, soaps made of higher fatty acids, i.e., mostly of fatty acids having 16 to 31 and preferably 16 to 18 carbon atoms per fatty acid radical, can be mixed with lower ester salts, i.e., with those whose fatty acid radicals have preferably 10 to 14 carbon atoms. The chain-length distribution can also be made just the opposite.

The substantially saturated hydrophobic radicals of sulfo-fatty acids contained in the ester salts may be straight-chained or branched. The sulfo-fatty acid group is in the alpha position, in contrast to those sulfo-fatty acids which are obtained by the sulfonation of unsaturated fatty acids and/or fatty acids containing hydroxyl groups.

The ratio and quantities of soap and ester salts varies widely and is governed by the intended application of the preparations of the invention. For example, if a better dispersion of subsequently formed calcium soaps is desired, amounts of 2 to 15 percent, and preferably from 3 to 10 percent, of the weight of the soap and ester sulfonate mixture will suffice. If the washing and cleaning effect of the preparations is based largely on the ester sulfonates, the latter are used in quantities of 15 to 80 percent, and preferably of 30 to percent, of the weight of the soap and ester salt mixture.

The previously mentioned other wash-active substances which may be present in addition to soap, ester salts and di-salts include non-ionic surfactants, especially the addition products of ethylene oxide and fatty alcohols, alkyl phenols and high-molecular-weight polypropylene glycols. These products are used primarily in conjunction with synthetic anionic surfactants of the sulfate or sulfonate type, and soap, in low-sudsing surfactant compounds.

The wash-active substance combinations according to the invention are non-transparent pastes, or more or less turbid solutions, or even clear solutions, depending on their concentration. Often the turbidity does not appear until after relatively long storage. This, however, does not affect the use of the pastes of solutions, because, when, for example, they are used as liquid detergents, other substances causing tunbidity may be contained in them in a dissolved or suspended state.

On account of their reduced viscosity, the wash-active substance combinations, according to the invention, are especially suitable for use with additional substances such as those employed in washing and cleansing operations and include the carbonates, ortho-phosphates, anhydrous phosphates (pyro-phosphates, polyphopsphates and polymetaphosphates) and the silicates of the alkalies, as well as other conventional washing alkalies. The organic chelate formers of the prior art can also be included in the preparations of the invention. Lastly, organic or inorganic colloids, water-soluble substances of high molecular weight, etc., can be added to them, such as those which serve, for example, as dirt carriers in the washing process. Water-soluble salts of polyacrylic acid or polymethacrylic acid, water-soluble derivatives of cellulose or starch, such as carboxymethylcellulose and ethers made from cellulose and oxyalkylsulfonic acids, and also the cellulose sulfates may be mentioned in this connection.

The total WAS concentration of the pastes or solutions of the invention may range from 5 to 55, and preferably from 10 to 30, percent of the weight of the total solution or paste. No components other than water need to be present.

The detergent combinations, according to the invention, may also contain conventional solubilizers, such as watersoluble organic solvents, or, more specifically, monovalent of polyvalent alcohols, in addition to ethers made of the same or different polyvalent alcohols, or optionally the partial ethers of polyvalent and monovalent alcohols. These include, for example, the aliphatic monovalent alcohols containing 1 to 5 carbon atoms, glycols with 2 to 5 carbon atoms, dior triethylene glycol, glycerine, polyglycerines and partial ethers of all these polyvalent alcohols with aliphatic, monovalent alcohols containing 1 to 4 carbon atoms in the molecule.

Liquid detergents and cleansers based on the washactive substance combinations of the invention having a content of non-surfactant accompanying substances, have approximately the following composition:

5-25 percent, preferably 7-20 percent, by Weight, of

wash-active substance combination 5-45 percent, preferably 10-30 percent, by weight, of

non-surfactant accompanying substances, such as:

-45 percent, preferably -30 weight percent of anhydrous phosphates or organic chelating agents, preferably pyrophosphates or polyphosphates;

0-6 percent, preferably 2-5 Weight percent of alkali silicates;

0-5 percent, preferably 0.5 to 2 weight percent of foam stabilizers, such as fatty acid amides or fatty acid alkylolamides;

0-10 percent, preferably 2-4 weight percent of solubilizers;

0-10 weight percent of neutrally reacting salts, especially inorganic salts, such as Na SO and/or NaCl and/or NaNO Balance, water.

. By varying the formulas within the above-stated limits, or by the selection of appropriate cations or combinations of cations, liquid washing and cleansing agents can be produced, which contain all of their ingredients in solution or in a non-settling suspension.

The following non-limiting examples are given as certain preferred embodiments of the invention and are not to be construed as narrowing the novel and inventive method and composition of the applicant.

Examples The components of the liquid or paste concentrates of wash-active substances are combined in the form of their technical crude products, either as aqueous pastes or as dry products, in the percentage composition (weight percentage) stated in each case. They are then adjusted with water to the desired concentration and completely dissolved by heating. The clear solutions are bottled in sealed containers and stored for three to four weeks. The concentrates thus obtained exhibit structural viscosity, which varies during storage, however, the variation decreases in the course of time and is almost negligible after three to four weeks. The change of viscosity is often accompanied by the formation of turbidity or precipitates and losses of homogeneity. These phenomena (change of the viscosity and losses of homogeneity) come to an end after three to four weeks; they can be observed both in the case of preparation-s containing disalts and in the c-ase of disalt-free examples. The viscosity reduction obtained by the invention is apparent, both immediately after the preparations are made, and after storage for relatively long periods.

Whenever the precipitates or inhomogeneities settle, the preparations are stirred before the viscosity is measured. The absolute values of the viscosities of the washactive substance concentrates depend to some extent on the structure and the composition of the starting products used for their manufacture; for example, the salt content of the technical washactive substances has an influence. For this reason, precise comparisons of viscosities-are possible only in the case of products which have been made from identical starting materials (i.e., from the same charge of a soap, or of a synthetic detergent) and have been treated in the same manner. In the following tables, such comparison is possible only in products having the same example number. The variations in the absolute values of the viscosities of similarly composed products which can be observed due to this circumstance are nevertheless small in comparison to the viscosity reduction achieved according to the invention.

Unless otherwise specified in the following tables, the anionic surfactants mentioned therein are sodium salts, and in the case of the sulfo-fatty acid salts, they are disodium salts. Ester salts and disalts are identified by the chain length or by stating the origin of the fatty acids, followed by a suflix. In the case of the disalts, the sufiix is /Di; in the case of the ester salts, the sufiix is a numeral which indicates the chain length of the alcohol radical. Accordingly, C /Di signifies the disalt of sulfolauric acid, while HPK/l. symbolizes the sulfonate made from hydrogenated palm kernel fatty acid methyl ester.

All of the HPK products described herein were made from a fatty acid fraction ofthe following composition:

Approx. wt. percent Laurie acid 58 Myristic acid 20 Palmitic acid 9 Stearic acid 13 or from an ester of this fatty acidrnixture. This fatty acid composition corresponds approximately to the C to C fraction of hydrogenated coconut or palm kernel fatty acid, or mixtures of these fractions.

Different charges of fatty acid mixtures of the following make-up are used to make the soap:

Identifying letter of the soap L S B Iodine Number Make-up of the Fatty Acid Wt. percent of fatty acid of chain length:

C3 to C14 -81 -40 -30 Of which C 2 forms -48 -27 -21 w-Cis -19 CZIFCH- -51 Of which 02 forms -42 -81=approximately 81.

TABLE I Example WAS Combination Viscosity Measurement Substance Wt. percent Spindle Cp./20 C.

It can therefore be seen from the above examples that the inclusion of small quantities of disalts of sulfofatty acids reduces the viscosity of commercially available soap to a greater extent than the ester salts of hydrogenated coconut or palm kernel fatty acids (HPK/l.), and that the combination of the disalts and diesters results in a synergistic effect, i.e., the viscosity when using the combination is less than that which would be expected from the individual ingredients.

The results outlined in Table II also indicate the viscosity-reducing properties of the disalts of this invention, and Example 2e above illustrates a synergistic effect obtained utilizing disalts and sodium sulfate.

It may also be seen that increasing quantities of ester salts increase the viscosity of the composition when the ester salt is utilized as the principal wash-active substance.

The above results also demonstrate the effectiveness of the disalts of this invention as an agent for reducing the viscosity of saponaceous materials, as contrasted to ester salts.

TABLE IV Exlarrnple WAS Combination Viscosity Measurement Substance Wt. percent Spindle Cp.l20 C.

5 1 20 150 5 1 12A 7 5 t 9 12A 2 2.1 Soap S 5 Nonionie 1 2. 5 12A 3 1. 45 1. 05 4e Soap S 5 sar a P g Nonionic 1 4 550 *lProduct formed by the addition of mots of ethylene oxide onto me of a technical oleyl alcohol (Iodine No. 50).

TABLE V Exla mple WAS Combination Viscosity Measurement Substance Wt. percent Spindle CpJ20 C.

Soap S 20 Nonionic 5 (1) gimp S 2g omomc cit/Dr..." 2.9 4 (8314-1815 1. 2%- 1 5c oap Nonionic 5 HPK/l. 2. 5 4 5, 250 Cit/Di. 1.45 Cn-is/DL 1.05

A stifi paste which could not be measuredwith the viscosimeter use 4O 2 Same as in Example 4.

The viscosities of various combinations of soaps, nonionic detergents and, in some instances, ester salts may also be reduced by the method and composition of this invention, as illustrated by the results outlined in Tables IV and V above.

The viscosity reductions obtained using 10-to-12- carbon-atom sulfo-fatty acid disalts and the disalts of hydrogenated palm kernel oil are illustrated in Table VI below. The results thus obtained indicate that, in some instances, 12-carbon-atorn sulfo-fatty acid disal-ts have a more pronounced effect on viscosity reduction than the lO-carbon-atom analogues.

The viscosities of the preparations of Examples 6 to 8 below are measured after four days of storage.

TABLE VI Exlaxmple WAS Combination Viscosity Measurement Substance Wt. percent Spindle Cp./20" G.

g 20 280 5 20 g 2e 02 10 4 1, 750 30 4 4, 650 g 20 102 35 1 Same as in Example 5.

The viscosities of the preparations of Examples 9 and 10 are measured after standing overnight.

TABLE VII Example WAS Combination Viscosity Measurement Substance Wt. percent Spindle Op [20 C.

2.9 12A 9 2.1 Soap O... 20 4 2, 600

The results of Examples 9a to 100, as illustrated in Table VII above, further demonstate the ability of disalts to reduce the viscosity of soap compositions. The results in Table VII also indicate that, in some instances, low ratios of disalts to soap are more effective.

Thus, there has been described a novel method and composition for the reduction of the viscosity of various saponaceous combinations of detergent substances in liquid or paste form by means of a disalt of a-sulfo-fatty acids having 10 to 12 carbon atoms in the fatty-acid radical, as exemplified by the alkali metal disalts of sulfolauric acid.

Although the invention has been described with reference to certain preferred embodiments, it is not the intention of the applicant to be limited thereby, and certain obvious modifications of the novel composition of matter and method are intended to be included within the broad scope of the invention, as embodied in the following claims.

The ester salts, disalts and any other salt-like WAS compounds that may be present may be in the form of sodium salts or in the form of the salts of other cations. Such other cations are, in addition to potassium, lithium and ammonium, organic bases such as mono-, dior triethanolamine. For the manufacture of wash-active substance combinations which contain practically no undissolved component-s, it may be advantageous to see to it that a plurality of cations is present simultaneously: for example, sodium and potassium salts can be used together, or potassium and triethanolamine salts, or sodium and potassium and triethanolamine salts.

What is claimed is:

1. Wash-active aqueous concentrate having a liquid to pasty consistency which consists essentially of (a) -55% of wash active substances constituting a mixture of fatty acid soaps having -31 carbon atoms in the fatty acid radicals and a-sulfofatty acid salts having 10 to 12 carbon atoms in the fatty acid radical, in which said a-sulfofatty acid salts are present in an amount of about 4-60% of said mixture; and

(b) 95-45% of water.

2. Concentrate according to claim 1 wherein said mixture includes, as further wash active substances, a-sulfonated fatty acid aliphatic ester salts having 10 to 22 carbon atoms in the corresponding a-sulfofatty acid radical and 1 to 4 carbon atoms in the corresponding aliphatic ester radical, said ester salts constituting 2 to 80% of the combined content of such ester salts and said fatty acid soaps, and said fatty acid soaps constituting at least about 25 of the total wash active substances present.

3. Concentrate according to claim 1 wherein said ocsulfofatty acid salts constitute about 10 to 30% of the total wash active substances present.

4. Concentrate according to claim 1 wherein said miX- ture includes a-sulfofatty acid salts having 10 to 18 carbon atoms in the fatty acid radical, at least 50% thereof being said u-sulfofatty acid salts having 10 to 12 carbon atoms in the fatty acid radical.

5. Concentrate according to claim 4 wherein at least two such a-sulfofatty acid salts are present which have fatty acid radicals which differ from each other and from said u-sulfofatty acid salts having 10 to 12 carbon atoms, said at least two such a-sulfofatty acid salts together correspondingly representing at most 50% of the total a-sulfofatty acid salts present.

6. Concentrate according to claim 1 wherein said fatty acid soaps have 12 to 18 carbon atoms in the fatty acid radical.

7. Concentrate according to claim 6 wherein at most 50% of said fatty acid soaps have unsaturated fatty acid radicals, said unsaturated fatty acid radicals corresponding to fatty acids having an iodine number of at most 40.

8. Concentrate according to claim 1 wherein more than 50% of said fatty acid soaps have 10-14 carbon atoms in the fatty acid radical.

9. Concentrate according to claim 1 wherein more than 50% of said fatty acid soaps have 16-31 carbon atoms in the fatty acid radical.

10. Concentrate according to claim 1 wherein 5-60% of said fatty acid soaps have 20-31 carbon atoms in the fatty acid radical.

11. Concentrate according to claim 1 wherein at least one supplemental washing and cleansing substance is present which is selected from the group consisting of neutrally reacting inorganic salts, alkali carbonates, alkali orthophosphates, anhydrous alkali phosphates, alkali silicates, organic chelate formers, foam stabilizers, dirt carriers, and water-soluble organic solvents.

12. Method of improving the viscosity of a wash active aqueous concentrate having a liquid to pasty consistency and consisting essentially of fatty acid soaps having 10-31 carbon atoms in the fatty acid radicals, which comprises admixing such concentrate with a-sulfofatty acid salts having 10-12 carbon atoms in the fatty acid radical in a quantity sufficient to provide a resulting wash active mixture in which the a-sulfofatty acid salts are present in an amount of about 4-60% of said mixture, and in which the improved viscosity concentrate consists essentially of -55% of such wash active mixture and -45% of water, with heating of at least one of the mixture components to dissolve at least some of the resulting mass in the water present.

13. Method according to claim 12 wherein said mixture includes, as further wash active substances, oc-Slllfonated fatty acid aliphatic ester salts having 10-22 carbon atoms in the corresponding a-sulfofatty acid radical and 1-4 carbon atoms in the corresponding aliphatic ester radical, said ester salts constituting 2-80% of the combined content of such ester salts and said fatty acid soaps, and said fatty acid soaps constituting at least about 25% of the total wash active substances present, and wherein the resulting improved viscosity concentrate i thereafter recovered.

14. Method according to claim 12 wherein said mixture includes u-sulfofatty acid salts having 10-18 carbon atoms in the fatty acid radical, at least 50% thereof being a-sulfofatty acid salts having 19-12 carbon atoms in the fatty acid radical.

References Cited UNITED STATES PATENTS 2,303,212 11/1942 Kise et al. 252121 2,915,473 12/1959 StirtOn et al. 252161 FOREIGN PATENTS 635,321 1/1962 Canada. 911,214 11/1962 Great Britain.

LEON D. ROSDOL, Primary Examiner. S. D. SCHNEIDER, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 ,377 ,289 April 9 1968 Werner Stein et a1.

It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1 line 52 "sulfoluaric" should read sulfolauric Column 4 line 46 "polyphopsphates" should read polyphosphates Column 8 TABLE IV, footnote thereof "lProduct formed by the addition of 10 mols of ethylene oxide onto 1 mo of a technical oleyl alcohol (Iodine No 50) should read Product formed by the addition of 10 mols of ethylene oxide onto 1 mol of a technical oleyl alcohol (Iodine No. 50) Column 9 TABLE VII second column, line 4 thereof "C 18/Di" should read C /Di Column 10 line 58 "19-12" should read 10-12 Signed and sealed this 25th day of November 1969 (SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR. Attesting Officer Commissioner of Patents 

1. WASH-ACTIVE AQUEOUS CONCNETRATE HAVING A LIQUID TO PASTY CONSISTENCY WHICH CONSISTS ESSENTIALLY OF (A) 5-55% OF WAH ACTIVE SUBSTANCES CONSTITUTING A MIXTURE OF FATTY ACID SOAPS HAIVNG 10-31 CARBON ATOMS IN THE FATTY ACID RADICALS AND A-SULFOATTY ACID SALTS HAVING 10 TO 12 CARBON ATOMS IN THE FATTY ACID RADICAL, IN WHICH SAID A-SULFOFATTY ACID SALTS ARE PRESENT IN AN AMOUNT OF ABOUT 4-60% OF SAID MIXTURE; AND (B) 95-45% OF WATER. 